CN104412433A - Sheet, electrode and fuel cell - Google Patents
Sheet, electrode and fuel cell Download PDFInfo
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- CN104412433A CN104412433A CN201380035373.6A CN201380035373A CN104412433A CN 104412433 A CN104412433 A CN 104412433A CN 201380035373 A CN201380035373 A CN 201380035373A CN 104412433 A CN104412433 A CN 104412433A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The purpose of the present invention is to provide: a sheet which exhibits high thicknesswise conductivity and excellent gas permeability, water repellency, corrosion resistance and flexibility and which is suitable for use in an electrode of a fuel cell or the like; an electrode; and a fuel cell. The present invention is a sheet which comprises a polytetrafluoroethylene, carbon black and graphite and which is characterized in that: the polytetrafluoroethylene has a standard specific gravity of 2.14 to 2.28; and the total amount of the carbon black and the graphite exceeds 35 mass% of the total amount of the polytetrafluoroethylene, the carbon black and the graphite.
Description
Technical field
The present invention relates to sheet material, electrode and fuel cell.More specifically, the present invention relates to the sheet material being suitable for fuel cell electrode, the electrode formed by this sheet material and there is the fuel cell of this electrode.
Background technology
Fuel cell has the membrane-electrode complex (MEA) be made up of the anode of the reaction playing electricity generate function and the electrode of negative electrode and the dielectric film of ion conductor that becomes between anode and negative electrode usually, and this MEA is formed for unit with the compartment clipped by dividing plate.At this, electrode is made up of the electrode catalyst layer promoting gas to spread and to carry out collecting (confession) electric electrode base material (also referred to as gas-diffusion electrode or collector body) and in fact becoming electrochemical reaction field.Such as at the anode of polymer electrolyte fuel cell, the fuel such as hydrogen react at the catalyst layer of anode and generate proton and electronics, and electrical conductivity is to electrode base material, and proton conducts to polymer solid electrolyte.Therefore, for anode, require that gas diffusibility (gas permeability), electronic conductivity (conductivity), ionic conductivity are good.On the other hand, at negative electrode, the oxidizing gas such as oxygen or air to react generation water at catalyst layer and the proton to be conducted by polymer solid electrolyte and the electronics conducted by electrode base material of negative electrode.The water generated can hinder close to dielectric film of hydrogen or air, therefore negative electrode not only wants gas diffusibility (gas permeability), electronic conductivity, ionic conductivity excellent, but also needs to discharge generated water (water proofing property, drainage) efficiently.In addition, electrode at high temperature can be exposed to water, oxygen, big current, therefore also needs excellent corrosion resistance.
As the electrode raw material of fuel cell etc., the material adding electroconductive stuffing in fine polytetrafluoroethylpowder powder receives publicity.But there are the following problems for existing commercially available product: be difficult to by paste-extruded etc. carry out shaping or for too low etc. for electrode conductivity.In addition, when usually manufacturing electrode by conductive sheet, in the mixture of polytetrafluoroethylene and electroconductive stuffing, add suitable extrusion aid carry out paste-extruded, and carry out sheet material by rolling etc.But although the conductivity of the method rolling direction is high, there are the following problems: for the thickness direction of sheet material, specific insulation exceeds close to an order of magnitude, poorly conductive.
As the concrete example of mixture using polytetrafluoroethylene and electroconductive stuffing, disclose the electrode (for example, see patent documentation 1) using polytetrafluoroethylene and carbon black.But there is the insufficient such problem of conductivity in this electrode.
In addition, the electrode (for example, see patent documentation 2) using carbon fiber weaving cloth and polytetrafluoroethylene is also disclosed.But except easily breaking, except the such problem of resistance to load difference, also there is the high such problem of cost of carbon fiber in this electrode.
In addition, the conductive material (graphite, carbon fiber and/or metal dust) beyond polytetrafluoroethylgranule granule, carbon black and this carbon black obtained by emulsion polymerisation is also disclosed with the powder (for example, see patent documentation 3) containing polytetrafluoroethylene of specific ratio mixture.In patent documentation 3, disclose this powder containing polytetrafluoroethylene to be obtained by the common condensation of polytetrafluoroethylgranule granule, carbon black and conductive material, and describe the conductivity of this powder, resistance to load is excellent, and cheap and be suitable at the high electrode of the conductivity of thickness direction.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-166520 publication
Patent documentation 2: Japanese Unexamined Patent Publication 7-201346 publication
Patent documentation 3: Japan Patent No. 4000915 specification
Summary of the invention
Invent problem to be solved
As mentioned above, various research being carried out to the material of the electrode that can be suitable for fuel cell etc., in order to realize higher levels of various desirable characteristics, also there is the leeway of research.
Especially, be strongly required while maintaining excellent gas permeability, water proofing property and corrosion resistance, realize the high conductivity of in the past above high conductivity, wherein especially thickness direction.
In addition, when manufacturing battery, in order to not produce breakage when electrode being pressed on catalyst layer or dividing plate, the flexibility making electrode have appropriateness is also important.
The present invention completes in view of above-mentioned present situation, its object is to provide sheet material, electrode and fuel cell, this sheet material has high conductivity at thickness direction, and gas permeability, water proofing property, corrosion resistance and flexibility are also excellent, can be suitable for the electrode of fuel cell etc.
For the means of dealing with problems
The sheet material of the present inventor to the electrode being suitable for fuel cell etc. carries out various research, find in the sheet material containing polytetrafluoroethylene, carbon black and graphite, when making the total amount of carbon black and graphite exceed 35 quality % of the total amount of polytetrafluoroethylene, carbon black and graphite, effectively can improve the conductivity of the thickness direction of sheet material.The present inventor also finds that this sheet material possesses the such characteristic of flexibility of gas permeability, water proofing property, corrosion resistance, appropriateness simultaneously.Further, also find that this sheet material is exceedingly useful as the electrode material of fuel cell etc., thus reached the present invention.
Namely, the present invention is a kind of sheet material, and it is the sheet material containing polytetrafluoroethylene, carbon black and graphite, it is characterized in that, the standard specific gravity of above-mentioned polytetrafluoroethylene is 2.14 ~ 2.28, and the total amount of carbon black and graphite exceedes 35 quality % of the total amount of polytetrafluoroethylene, carbon black and graphite.
The mass ratio of above-mentioned carbon black and above-mentioned graphite is preferably 99/1 ~ 30/70.
Above-mentioned polytetrafluoroethylene is preferably proplast or modified Teflon, is below the 0.02 quality % of whole polymerized unit in described modified Teflon based on the polymerized unit of modified monomer.
The standard specific gravity of above-mentioned polytetrafluoroethylene is preferably 2.14 ~ 2.22.
Preferred above-mentioned polytetrafluoroethylene, carbon black and graphite are by being total to condensation thus the sheet material mixed.
The average grain diameter of above-mentioned carbon black is preferably below 70nm.
The average grain diameter of above-mentioned graphite is preferably less than 50 μm.
Above-mentioned graphite is preferably flakey or tabular.
The invention still further relates to a kind of electrode, it is characterized in that, it comprises above-mentioned sheet material.
The invention still further relates to a kind of fuel cell, it is characterized in that, it has above-mentioned electrode.
The present invention is described in detail below.
Sheet material of the present invention contains polytetrafluoroethylene [PTFE].Thus, sheet material becomes the material of water proofing property, corrosion resistance and flexibility excellence.
Above-mentioned polytetrafluoroethylene refers to the proplast [TFE homopolymers] and/or modified Teflon [modified ptfe] with fibril voltinism and non melt processable.In this manual, above-mentioned " modified ptfe " refers to the copolymer obtained by copolymerization as monomer component containing tetrafluoroethene [TFE] and a small amount of modified monomer.In this manual, describe be defined in TFE homopolymers but not modified ptfe when, do not use " polytetrafluoroethylene " as term.
Even if the aspect being also easy to sheet material from the aspect being easy to porous materialization and the addition that increases carbon black and graphite because being easy to fibrillation is considered, as above-mentioned polytetrafluoroethylene, being preferably proplast or modified Teflon, is below the 0.02 quality % of whole polymerized unit based on the polymerized unit of modified monomer in described modified Teflon.
When above-mentioned polytetrafluoroethylene is modified ptfe, as modified monomer, as long as just can be not particularly limited with the monomer of TFE copolymerization, the perfluoroolefines such as such as hexafluoropropylene [HFP] can be enumerated; Chlorotrifluoroethylene [CTFE]; The HF hydrocarbons such as trifluoro-ethylene; Perfluoroalkyl vinyl ether etc.
Be not particularly limited as above-mentioned perfluoroalkyl vinyl ether, can enumerate such as with following general formula (I):
CF
2＝CF-ORf(I)
The perfluor unsaturated compound etc. that (in formula, Rf represents full-fluorine group) represents.In this manual, " full-fluorine group " refers to and the alkyl that the hydrogen atom of carbon atom bonding is all replaced by fluorine atoms.Above-mentioned full-fluorine group can have ehter bond.
As above-mentioned perfluoroalkyl vinyl ether, Rf in such as above-mentioned general formula (I) can be enumerated and represent that carbon number is perfluor (alkyl vinyl ether) [PAVE] of the perfluoroalkyl of 1 ~ 10.The carbon number of above-mentioned perfluoroalkyl is preferably 1 ~ 5.
As the perfluoroalkyl in above-mentioned PAVE, such as perfluoro-methyl, perfluoro-ethyl, perfluoro propyl, perfluoro butyl, perfluoropentyl, perfluoro hexyl etc. can be enumerated, be preferably perfluoro propyl.
As above-mentioned perfluoroalkyl vinyl ether, can also enumerate perfluor (alkoxyalkyl vinyl ethers) or perfluor (alkyl polyoxy alkylidene vinyl ethers) etc., described perfluor (alkoxyalkyl vinyl ethers) or perfluor (alkyl polyoxy alkylidene vinyl ethers) are the materials that Rf represents following radicals in above-mentioned general formula (I): carbon number is the perfluor (alkoxyalkyl) of 4 ~ 9, the organic group that represents with following formula
[changing 1]
(in formula, m represents the integer of 0 or 1 ~ 4) or the organic group represented with following formula.
[changing 2]
(in formula, n represents the integer of 1 ~ 4)
Above-mentioned modified ptfe such as can be formed by the single resin formed, in addition also can for having the modified ptfe of nucleocapsid structure.
Above-mentioned nucleocapsid structure is existing known structure, refers to the structure of the primary particle in the aqueous liquid dispersion that can be manufactured by the method etc. recorded in United States Patent (USP) No. 6841594 specification.Such as, first tetrafluoroethene [TFE] and modified monomer are as required carried out polymerization to manufacture core part (TFE homopolymers or modified ptfe), then, tetrafluoroethene and modified monomer are as required carried out polymerization to manufacture shell part (TFE homopolymers or modified ptfe), can nucleocapsid structure be obtained thus.
Wherein, preferred core portion is TFE homopolymers and shell portion is the nucleocapsid structure of modified ptfe.
Above-mentioned nucleocapsid structure comprises following situation: (1) core portion and shell portion are obtained by different monomer compositions; (2) core portion and shell portion are obtained by same monomer composition and two-part standard specific gravity (SSG) is different; And (3) core portion and shell portion is obtained by different monomers composition and two-part standard specific gravity is also different.
As the above-mentioned modified ptfe with nucleocapsid structure, can enumerate and the monomer composition (TFE and modified monomer as required) for the manufacture of core portion and the monomer composition (TFE and modified monomer as required) for the manufacture of shell portion are carried out emulsion polymerisation thus with the material that the mode of emulsion obtains.Emulsion polymerisation can be undertaken by existing known method.As above-mentioned modified monomer, the monomer same with above-mentioned modified monomer can be used.
The ratio (modification amount (quality %)) of whole polymerized unit (namely based on the polymerized unit (TFE unit) of TFE and the total amount of modified monomer unit) is accounted for based on the polymerized unit (modified monomer unit) of modified monomer relevant with the kind of above-mentioned modified monomer in above-mentioned modified ptfe, but be preferably small amount, this small amount is the degree can not giving melt fluidity to modified ptfe, be preferably below 0.05 quality %, be more preferably below 0.02 quality %, and be preferably more than 0.0001 quality %.In addition, become easy viewpoint from the porous materialization made during above-mentioned modified ptfe sheet material, also the ratio of preferred above-mentioned modified monomer unit is less.Such as, when using above-mentioned perfluoroalkyl vinyl ether as above-mentioned modified monomer, the preferred upper limit is 0.05 quality %, and preferred lower limit is 0.001 quality %.In addition, such as, when using hexafluoropropylene as above-mentioned modified monomer, the preferred upper limit is 0.05 quality %, and preferred lower limit is 0.001 quality %.
The standard specific gravity (SSG) of above-mentioned polytetrafluoroethylene is 2.14 ~ 2.28.When the standard specific gravity of above-mentioned polytetrafluoroethylene is in above-mentioned scope, the mechanical strength of the sheet material obtained becomes good, even and if when containing a large amount of carbon black and graphite, the mechanical strength of sheet material is also large.Further, even if when containing a large amount of carbon black and graphite, be also easy to sheet material.When standard specific gravity is excessive, be likely difficult to sheet material.Above-mentioned standard specific gravity is preferably 2.14 ~ 2.22.The preferred upper limit of above-mentioned standard specific gravity is 2.18, the preferred upper limit is 2.17 further, further preferably the upper limit is 2.165.
Above-mentioned standard specific gravity (SSG) measures according to ASTM D 4895-89 the value obtained.The less then molecular weight of above-mentioned standard specific gravity is higher.
The fusing point of above-mentioned polytetrafluoroethylene is preferably 327 ~ 345 DEG C.Above-mentioned fusing point makes the programming rate of means of differential scanning calorimetry (DSC) be 10 DEG C/min to measure the value obtained.
Sheet material of the present invention preferably contains more than 20 quality % relative to the total amount of polytetrafluoroethylene, carbon black and graphite and is less than the polytetrafluoroethylene of 65 quality %.When polytetrafluoroethylene is too much, the conductivity of the thickness direction of sheet material is likely not high enough; Time very few, be likely difficult to by stretching described later or extrude processing and carry out sheet material.The preferred upper limit is 60 quality %, the further preferred upper limit is 55 quality %.In addition, preferred lower limit is 30 quality %, further preferred lower limit is 40 quality %.
Sheet material of the present invention contains carbon black and graphite.
Above-mentioned carbon black is the conductive material of the spherical or chain of the micro mist generated by gas phase thermal decomposition or the imperfect combustion of natural gas, hydrocarbon gas.As above-mentioned carbon black, furnace black, channel black, acetylene black, thermals etc. can be enumerated.Wherein, from the view point of obtaining high conductivity, be preferably acetylene black, furnace black.
From the view point of giving high conductivity to obtained sheet material, the average grain diameter of above-mentioned carbon black is preferably below 70nm.The preferred upper limit is 55nm.In addition, preferred lower limit is 10nm, preferred lower limit is 20nm.Above-mentioned average grain diameter is the value calculated according to the particle size distribution obtained by the automatic particle size distribution device of ultracentrifugation formula (hole field makes CAPA-700, rotating speed 700rpm, the medium that Co., Ltd. of institute manufactures: pure water, temperature: room temperature) mensuration.
In addition, the preferred dibutyl phthalate of above-mentioned carbon black (DBP) oil absorption is 100cm
3/ more than 100g.The carbon black with the DBP oil absorption of above-mentioned scope is high structure, can give high conductivity to obtained sheet material.The preferred lower limit of above-mentioned DBP oil absorption is 110cm
3/ 100g.Above-mentioned DBP oil absorption can measure based on JIS K6217-4.
Above-mentioned graphite (graphite) is also called blacklead, has the layer structure belonging to hexagonal crystal system, is the aspect that forms hexagonal huge wire side by weak Van der Waals key lamination.
As the shape of above-mentioned graphite, spherical, flakey, tabular, amorphous etc. can be enumerated, but be preferably flakey or tabular.In order to improve the conductivity of sheet material, the use amount increasing carbon black can be considered, but the apparent density of carbon black be low, if therefore excessively increase use amount, the factor that sheet formability is reduced may be become.But, by share the graphite of flakey or tabular, mouldability can be improved when not causing sheet material conductivity and reducing.
In this manual, graphite is that flakey or tabular refer to that the most minor axis in graphite is overall with more than 50 quality % is 0.5 ~ 10 μm and most major diameter is the graphite of 1 ~ 200 μm.Most minor axis and the most major diameter of above-mentioned graphite are the values measured by scanning electron microscopy (SEM).
Above-mentioned graphite be flakey or tabular when, preferred draw ratio (flat ratio) is more than 5.Above-mentioned draw ratio refers to the ratio (most major diameter/most minor axis) of the most major diameter of flakey or plate shaped graphite relative to most minor axis.Above-mentioned draw ratio can calculate according to the most major diameter utilizing scanning electron microscopy (SEM) to measure and most minor axis, adopts the mean value to the draw ratio that 5 sample determinations obtain.
The preferred average grain diameter of above-mentioned graphite is less than 50 μm.The specific area with the graphite of the average grain diameter of above-mentioned scope is large, can give high conductivity to obtained sheet material.Above-mentioned average grain diameter is more preferably less than 30 μm, more preferably less than 20 μm.In addition, above-mentioned average grain diameter is preferably greater than 1 μm, more preferably greater than 5 μm.Above-mentioned average grain diameter is according to utilizing the automatic particle size distribution device of ultracentrifugation formula (hole field makes CAPA-700, rotating speed 700rpm, the medium that institute Co., Ltd. manufactures: pure water, temperature: room temperature) to measure the particle size distribution obtained and the value calculated.
In sheet material of the present invention, the total amount of carbon black and graphite exceedes 35 quality % of the total amount of polytetrafluoroethylene, carbon black and graphite.When the total amount of carbon black and graphite is very few, the conductivity of the thickness direction of sheet material is likely not high enough; Time too much, be likely difficult to by stretching described later or extrude processing and carry out sheet material.Preferred lower limit is 40 quality %, preferred lower limit is 50 quality %.In addition, the preferred upper limit is 80 quality %, the preferred upper limit be 70 quality %, the further preferred upper limit is 65 quality %.
In addition, the mass ratio of carbon black and graphite is preferably 99/1 ~ 30/70.Be more preferably 95/5 ~ 70/30.
As long as sheet material of the present invention, containing above-mentioned polytetrafluoroethylene, above-mentioned carbon black and above-mentioned graphite, also can contain other composition further.
From the viewpoint of can give more high conductivity to obtained sheet material, sheet material of the present invention is preferably further containing carbon fiber.Organic polymer fibers carbonization obtains by above-mentioned carbon fiber.Be not particularly limited as above-mentioned organic polymer fiber, such as cellulose fibre, polyacrylonitrile [PAN] series fiber, vinylon series fiber, heat resistant fibre etc. can be enumerated, in the present invention, preferred use has the carbon fiber of conductivity, as the carbon fiber with conductivity, be preferably PAN series fiber.
When sheet material of the present invention contains carbon fiber, the content of carbon fiber is preferably 0.5 ~ 10 quality % of the total amount of carbon black, graphite and carbon fiber.
Sheet material of the present invention can manufacture as follows: after preparing the sheet material composition containing polytetrafluoroethylene, carbon black, graphite and other composition (such as carbon fiber) as required, use this sheet material composition to carry out sheet material, manufacture sheet material of the present invention thus.Above-mentioned sheet material composition can become assign to be prepared by mixed carbon black in the polytetrafluoroethylene obtained via emulsion polymerisation or suspension polymerisation, graphite and as required other.
When obtaining above-mentioned polytetrafluoroethylene by emulsion polymerisation, the polytetrafluoroethylene obtained is formed as the latex being dispersed with polymer beads after the polymerization reaction based on emulsion polymerisation terminates.Sometimes also the polymer beads in this latex is called latex particle or primary particle.Usually, the average grain diameter of this primary particle is 0.1 ~ 0.5 μm.After terminating based on the polymerization reaction of emulsion polymerisation, after latex particle being carried out condensation, suitably cleaning, carry out drying and pulverize as required, so talking about and can obtain fine polytetrafluoroethylpowder powder.Sometimes also the particle of the polymer obtained above by condensation is called second particle, usual average grain diameter is 20 ~ 1000 μm.
Method as above-mentioned condensation is not particularly limited, and can use and such as after the interpolation electrolyte such as inorganic salts, acid or the water-miscible organic solvent such as methyl alcohol, acetone, carry out the existing known methods such as vigorous stirring, preferably uses above-mentioned stirring.From the viewpoint of easy condensation, for the latex of condensation preferably not containing nonionic surfactant and anionic surfactant.
Can in the fine polytetrafluoroethylpowder powder obtained as mentioned above mixed carbon black and graphite (and other composition) and obtain sheet material composition, but be dispersed in more fully in sheet material from the view point of making carbon black and graphite (and other composition), preferably after emulsion polymerisation, when making polytetrafluoroethylene carry out condensation, mixed carbon black and graphite (and other composition), obtain sheet material composition thus.That is, preferably by making polytetrafluoroethylene and carbon black and graphite (and other composition) carry out common condensation to obtain sheet material composition.
When carrying out common condensation, carbon black and graphite (and other composition) are added in the latex of the polytetrafluoroethylene obtained by emulsion polymerisation, then carry out condensation process.Be added on the surface that carbon black in latex and graphite (and other composition) are attached to the latex particle of polytetrafluoroethylene.There is cohesion by condensation process as primary particle and form second particle in latex particle, have carbon black and graphite (and other composition) in therefore obtained second particle in the interface of primary particle and primary particle under the state being so attached with carbon black and graphite (and other composition) from the teeth outwards.That is, second particle has carbon black and graphite (and other composition) therein.
From improving dispersiveness in the latex of polytetrafluoroethylene and the aspect be fully attached on the surface of latex particle, carbon black and graphite (and other composition) when carrying out common condensation preferably in the latex making an addition to polytetrafluoroethylene before be dispersed in water in advance.The method of above-mentioned dispersion can according to the kind of carbon black and graphite (and other composition), size carrys out Selection utilization blender, ball mill carries out vigorous stirring method etc.
Above-mentioned condensation is altogether carried out or is carried out under surfactant-free exists under the existence of surfactant, and above-mentioned surfactant is preferably below the 1 quality % of polytetrafluoroethylene.When above-mentioned surfactant is too much, in the common condensation of polytetrafluoroethylene and carbon black and graphite (and other composition), amount between polytetrafluoroethylene and the surfactant between carbon black and graphite (and other composition) is too much, and the latex particle of polytetrafluoroethylene is difficult to condensation occurs.Above-mentioned condensation altogether is more preferably carried out under surfactant-free exists.
The powder (sheet material composition) containing polytetrafluoroethylene obtained by common condensation can be the powder after pulverizing as mentioned above.Method as above-mentioned pulverizing is not particularly limited, such as, can be used in the pulverizer used in conventional pulverizing, also can particle diameter be made as required consistent.
The powder containing polytetrafluoroethylene so obtained can take into account the conductivity of obtained sheet material and resistance to load when using it to make sheet material.Not clear as the mechanism that can play advantageous effects so, but think as follows.
Namely think, when using the powder containing polytetrafluoroethylene obtained by common condensation to manufacture sheet material of the present invention, in manufacturing process, the material formed by the powder containing polytetrafluoroethylene is carried out to stretching described later, rolls or extrude, but by above-mentioned stretching, the external force of rolling or extruding, carbon black and graphite are blended in as mentioned above in the particle of polytetrafluoroethylene and become matrix, himself are subject to the external force stretching, roll or extrude simultaneously.By above-mentioned stretching, the external force of rolling or extruding, graphite himself does not stretch or stretches hardly, but carbon black himself stretches, and is changing into the shape (ought to also referred to as needle-like) of extending at above-mentioned external force direction.So stretched, to roll or the sheet material extruding and obtain has the carbon black maintaining original form or the graphite substantially do not deformed and elongated shape in inside, therefore when circulating current, carbon black bridged graphite, thus improve conductivity.
As mentioned above, the powder containing polytetrafluoroethylene obtained by common condensation has carbon black and graphite (and other composition) as second particle in inside, when therefore carrying out above-mentioned stretching or extrude, carbon black and graphite (and other composition) are well-dispersed in the granuloplastic matrix by polytetrafluoroethylene.Therefore, the excellent electric conductivity of the sheet material obtained, and not easily crack, resistance to load is excellent.
When obtaining above-mentioned polytetrafluoroethylene by suspension polymerisation, obtained former powder is temporarily ground into the size of tens ~ hundreds of μm, then carries out spheroidizing (granulation) and drying, obtain polytetrafluoroethylene molding powder thus.Sheet material composition can be obtained with dry type mixed carbon black and graphite (and other composition) in the polytetrafluoroethylene molding powder so obtained.
So, as above-mentioned polytetrafluoroethylene, can use any one in the polytetrafluoroethylene obtained by emulsion polymerisation, the polytetrafluoroethylene obtained by suspension polymerisation, but from the viewpoint of being easy to porous materialization during sheet material, preferably use the polytetrafluoroethylene obtained by emulsion polymerisation.
Above-mentioned sheet material composition can according to purposes further containing the various additives except polytetrafluoroethylene, carbon black, graphite and carbon fiber.Above-mentioned additive is not particularly limited, can enumerates when such as above-mentioned sheet material composition being used for paste-extruded and be often used in paste-extruded extrusion aid; Aluminium oxide, boron nitride, carborundum etc. have the particle of fire resistance; The hydrophilic particulate such as silicon dioxide, polyphenylene oxide, polyphenylene sulfide; The fillers etc. such as glass fibre.Further, also can according to required mixture other conductive material except carbon black, graphite and carbon fiber as above-mentioned additive.
When mixture has an extrusion aid, relative to the total amount of polytetrafluoroethylene, carbon black and graphite (if needing carbon fiber in addition), preferred mixture has the extrusion aid of 16 ~ 50 quality %.Be more preferably 30 ~ 40 quality %.
Sheet material of the present invention carries out sheet material preferably by the above-mentioned sheet material composition of use and obtains.In this manual, above-mentioned " sheet material " refers to and is shaped to sheet.Above-mentioned sheet not only comprises the shape being usually considered to sheet material, also comprise the such as various smooth or thin shape such as band shape, strip, membranaceous, T-shaped, C-shaped, E shape, also comprise the shape of these shapes being preserved with smooth state or other various forms such as helical form, winding.
Above-mentioned sheet material stretches or extrudes preferably by carrying out the sheet material carried out.Thus, sheet material has loose structure, and gas permeability is excellent, and the excellent electric conductivity of thickness direction.As the index of above-mentioned conductivity, have specific insulation, sheet material of the present invention passes through via above-mentioned stretching or extrudes manufacture, and the specific insulation of thickness direction can be made thus to be such as 0.1 below Ω cm.
Comprising under the prerequisite stretching or extrude, above-mentioned sheet materialization can also comprise other operation.
As the method for above-mentioned stretching, uniaxial tension, the existing known pulling method such as biaxial stretch-formed can be used.As the above-mentioned method extruded, plunger extrusion molding, paste-extruded method etc. can be used to be generally used for the existing known extrusion molding of polytetrafluoroethylene, be preferably paste-extruded method due to suitable fibrillatable can be carried out.
When above-mentioned sheet material composition contains the polytetrafluoroethylene obtained by emulsion polymerisation, above-mentioned sheet materialization preferably comprises following operation: this sheet material composition is processed into the sheet thicker than desired thickness via extruding and/or rolling, obtained sheet products formed is stretched to desired thickness under defined terms.As the example of this sheet material, the method such as comprising following operation can be enumerated: by paste-extruded by above-mentioned sheet material composition molding be cylindric after, the existing known rolling process such as to prolong by roll-in to roll, after volatilization removing extrusion aid, stretch under defined terms.
Above-mentioned calendering is preferably carried out at 40 ~ 100 DEG C.
Carry out at the temperature of above-mentioned stretching preferably more than 200 DEG C and below the fusing point of polytetrafluoroethylene.The preferred upper limit is 320 DEG C.In addition, preferably about 1.2 ~ 10 times are stretched at rolling direction.In addition, except rolling direction, also about 1.2 ~ 10 times can be stretched to transverse direction (being approximately perpendicular to the direction of rolling direction).
It should be noted that, above-mentioned stretching is preferably carried out unfired sheet products formed.Above-mentioned " unfired " refers to, when manufacturing products formed, does not carry out being heated to firing of the temperature more than fusing point of polytetrafluoroethylene.
When above-mentioned sheet material composition contains the polytetrafluoroethylene obtained by emulsion polymerisation, also can not carry out stretching and carrying out sheet material by extruding.In this case, after above-mentioned sheet material composition is extruded into the sheet of desired thickness, volatilization removing extrusion aid.Thus, in sheet material, there is the generation space, position of extrusion aid, therefore sheet material can have loose structure.Now, in order to generate the hole of sufficient size, preferably use than usual more extrusion aid.
When above-mentioned sheet material composition contains the polytetrafluoroethylene obtained by suspension polymerisation, above-mentioned sheet materialization preferably comprises following operation: by this sheet material composition via compression forming with fire and be processed into the sheet thicker than desired thickness, obtained sheet products formed is stretched to desired thickness under defined terms.In order to obtain above-mentioned sheet products formed, by above-mentioned compression forming, above-mentioned sheet material composition directly can be processed into sheet, also can such as be processed into cylindric by above-mentioned compression forming, fire, then scrape (Skiving) processing and fabricating by revolving and go out sheet products formed.It should be noted that, revolving and scrape processing and refer to following processing method: usually carrying out firing etc. the formed body that conventional method makes in advance after the shape such as cylindric to be installed on lathe by by compression forming being, according to the main points of radish peeling, formed body is rotated while cut film from the side, thus obtain sheet material or film.
Above-mentioned compression forming, fire and revolve and scrape processing and can carry out under existing known condition.Carry out at the temperature of above-mentioned stretching preferably more than 200 DEG C and below the fusing point of polytetrafluoroethylene.The preferred upper limit is 320 DEG C.In addition, be preferably stretched to about 1.1 ~ 5 times in a direction, be stretched to about 1.0 ~ 3 times at other direction (being such as approximately perpendicular to the direction in an above-mentioned direction) simultaneously.
When above-mentioned sheet material composition contains the polytetrafluoroethylene obtained by emulsion polymerisation with containing the polytetrafluoroethylene obtained by suspension polymerisation, above-mentioned sheet materialization all preferably comprises stretching process.
Sheet material of the present invention has high conductivity in a thickness direction.Specifically, the specific insulation of the thickness direction of above-mentioned sheet material is preferably 0.1 below Ω cm.If the specific insulation of thickness direction is in above-mentioned scope, then can obtain the sufficient conductivity required by electrode of fuel cell etc.As above-mentioned specific insulation, be more preferably 0.01 below Ω cm, more preferably 0.005 below Ω cm.
Above-mentioned specific insulation can use four probe method to measure.
In addition, the resistance value measured by method described later of sheet material of the present invention is preferably 0.13 below Ω.The preferred upper limit is 0.1 Ω.
Sheet material of the present invention has loose structure.That is, having can the space (hole) of circulated gases.Above-mentioned space is preferably dimensioned to be 0.1 ~ 5 μm.Be more preferably 0.4 ~ 2 μm, more preferably 0.7 ~ 1.5 μm.
The size in above-mentioned space can measure by using the pore distribution measurement device of Vesicular protein.
The thickness of above-mentioned sheet material is preferably less than 150 μm.When the thickness of sheet material is in above-mentioned scope, graphite can be more efficiently made to be exposed to the two-sided of sheet material.As the thickness of sheet material, be more preferably less than 120 μm, more preferably less than 100 μm.As the thickness of sheet material, be also preferably more than 50 μm, be more preferably more than 60 μm.
Sheet material of the present invention has high conductivity at thickness direction, and gas permeability, water proofing property, corrosion resistance and flexibility are also excellent, therefore, it is possible to for the raw material etc. of electrode material, heater widely in purposes.Wherein, the electrode of fuel cell etc. can be suitable for.Also be one of the present invention to comprise the electrode that sheet material of the present invention is feature.
Above-mentioned electrode is not particularly limited, such as electrode for fuel cell, hydrogen peroxide maker electrode, electrode for electrolysis, plating electrode, conventional batteries electrode etc. can be enumerated.Wherein, the gas diffusion layers electrode of electrode for fuel cell, especially fuel cell is preferably.
Above-mentioned electrode preferably comprises sheet material of the present invention and electrode catalyst layer, and this electrode can be used in anode, negative electrode in any one.At this, anode comprises anode catalyst layer, and has proton-conducting; Negative electrode comprises cathode catalyst layer, and has proton-conducting.By engaging sheet material of the present invention as gas diffusion layers on anode catalyst layer and cathode catalyst layer outer surface separately, form electrode of the present invention thus.
Above-mentioned anode catalyst layer comprises the catalyst being easy to fuel (such as hydrogen) oxidation to generate proton, and cathode catalyst layer comprises makes proton and electronics and oxidant (such as oxygen, air) react and generate the catalyst of water.For anode and negative electrode any one, be all applicable to using platinum or comprise platinum and ruthenium etc. alloy as catalyst, be preferably the catalyst granules of below 10 ~ 1000 dusts.In addition, this catalyst granules preferably supports the conductive particle in 0.01 ~ 10 μm of such side-to-side dimensions of furnace black, channel black, acetylene black, carbon black, active carbon, graphite.Catalyst granules be preferably 0.001mg/cm relative to the loading of catalyst layer projected area
2above, 10mg/cm
2below.
Above-mentioned electrode can be formed film/assembly of electrode (membrane/electrode assembly) (being often called " MEA ") together with solid polyelectrolyte membrane.As this film/assembly of electrode, can enumerate such as use electrode of the present invention as anode and negative electrode and between this anode and this negative electrode the closely sealed film/assembly of electrode maintaining polyelectrolyte membrane.
As above-mentioned polyelectrolyte, preferably there is the strong acid group such as sulfo group, phosphate; The organic polymer of the weak acid group isopolarity groups such as carboxyl.In addition; as organic polymer; the poly-aromatic condensation system macromolecule such as (4-phenoxybenzoyl-Isosorbide-5-Nitrae-phenylene), alkyl sulfonate polybenzimidazole of sulfonation, perfluorocarbon (Nafion (E.I.Du Pont Company's system: registered trade mark), ACIPLEX (Asahi Kasei Corporation's system)), carboxylic perfluorocarbon (FlemionS film (Asahi Glass Inc.: registered trade mark)) etc. containing sulfo group can be enumerated.
The manufacture method of MEA is such as specifically recorded in JOURNAL OF APPLIEDELECTROCHEMISTRY, 22 (1992) p.1-7 in.
Above-mentioned film/assembly of electrode such as can be used in polymer electrolyte fuel cell.Just be not particularly limited as long as above-mentioned solid macromolecular electrolyte type fuel cell has above-mentioned film/assembly of electrode, usually can comprise the constituent such as electrode, collector body, gas diffusion layers, dividing plate forming solid macromolecular electrolyte type fuel cell.
So, be also one of the present invention to have the fuel cell that electrode of the present invention is feature.
Invention effect
Sheet material of the present invention derives from above-mentioned formation, therefore has high conductivity at thickness direction, and gas permeability, water proofing property, corrosion resistance and flexibility are also excellent.Above-mentioned sheet material can be suitable for the gas diffusion layers electrode of electrode, the especially fuel cell of fuel cell etc.
Embodiment
By embodiment, the present invention will be described in more detail, but the invention is not restricted to these embodiments.
The assay method of various physical property is as described below.
(mensuration of standard specific gravity)
Standard specific gravity (SSG) measures according to ASTM D 4895-89.
(mensuration of resistance value)
The Copper Foil of placing 50 μm of thickness on the piece of stainless steel of 40mm × 40mm × 20mm.Conductive sheet (sample) is clipped in the bottom surface with 2mm × 8mm and length is between the bottom surface of the iron cuboid of 30mm and Copper Foil, utilize the power of 1600g that iron cuboid is attached to conductive sheet, measure the resistance value between iron cuboid and Copper Foil.The digital multimeter VOAC92 that resistance measuring instrument uses Iwagasaki Communication Equipment Co., Ltd. to manufacture.
Embodiment 1
Carbon black 3030B (the DBP oil absorption 130cm of water 1620g, Mitsubishi chemical Co., Ltd's manufacture is added in the polyethylene bottle of 5 liters
3/ 100g, average grain diameter 55nm) graphite BF-3AK (flaky graphite, average grain diameter the be 3 μm) 36g of Yueshi ink manufactured by industry stirring in 144g and Co., Ltd., prepares water-borne dispersions.Add in this water-borne dispersions containing standard specific gravity be 2.16 polytetrafluoroethylene (PTFE (modification amount 0.00 quality %)) and resinous principle be the PTFE water-borne dispersions 720g of 25 quality % and stir, make PTFE condensation thus, condensate is put into the moisture evaporation that drying oven carries out at 180 DEG C 10 hours, thus produce mixed-powder.
In this mixed powder 350g, mix the hydrocarbon system solvent IsoparG that 193g manufactures as the Exxon Mobil Corporation of paste-extruded shaping extrusion aid, carry out slaking in 10 hours.This auxiliary agent mixed-powder is carried out preforming, utilizes
machine barrel,
mandrel, mould internal diameter
paste-extruded machine extrude, result can be extruded with the extrusion pressure of 7 tons.Should
extrudate is heated to 70 DEG C, utilize 80 DEG C,
stack roll with six stages.This sheet material is heated 2 hours with 180 DEG C in electric furnace, makes extrusion aid evaporate thus.Further this sheet material is utilized biaxial stretcher with 250 DEG C, the condition of 500mm/ second is stretched to longitudinally 1.2 times, laterally 1.2 times, carry out firing for 5 minutes with 350 DEG C under state after the stretch, thus obtain the conductive sheet of 100mm × 180mm × 100 μm.Measure resistance value according to said determination method, result is 0.07 Ω.
Embodiment 2 ~ 5
According to the ratio (quality %) changing PTFE (modification amount 0.00 quality %), carbon black and graphite table 1 Suo Shi, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value.Show the result in table 1.
Comparative example 1
Make that the amount of carbon black is 180g, the amount of graphite is 0g, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value, result is 0.24 Ω.
Embodiment 6
Carbon black is become average grain diameter 30nm, DBP oil absorption 115cm
3the carbon black of/100g, produces the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value, result is 0.15 Ω.
Comparative example 2
The amount that the amount of carbon black is 260g, the amount of graphite is 0g, PTFE water-borne dispersions is made to be 228g, attempt to produce conductive sheet with the condition identical with embodiment 1 in addition, the paste-extruded article shaped of result is discontinuous, forms discontinuous uneven sheet material when calendering stretches.
Embodiment 7 ~ 8
According to the ratio (quality %) changing PTFE, carbon black and graphite table 1 Suo Shi, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value.Show the result in table 1.
Embodiment 9 ~ 10
Use Denka Black (trade name, powdery product, average grain diameter are 35nm, Deuki Kagaku Kogyo Co., Ltd's system) as carbon black, UCP (trade name, flaky graphite, draw ratio are more than 5, average grain diameter be more than 3 μm, Japanese graphite Industrial Co., Ltd system) as graphite, according to the ratio (quality %) changing PTFE, carbon black and graphite table 1 Suo Shi, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value.Show the result in table 1.
Embodiment 11
PTFE water-borne dispersions is become containing standard specific gravity be 2.16 PTFE (modification amount 0.00 quality %) and resinous principle be 28 quality %, nonionic surfactant is the PTFE water-borne dispersions of 0 quality %, according to the ratio (quality %) changing PTFE, carbon black and graphite table 1 Suo Shi, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value.Show the result in table 1.
Comparative example 3
PTFE water-borne dispersions is become and is the PTFE (modification amount 0.00 quality %) of 2.16 containing standard specific gravity and resinous principle is 28 quality %, nonionic surfactant and anionic surfactant is the PTFE water-borne dispersions of 0 quality %, according to the ratio (quality %) changing PTFE, carbon black and graphite table 1 Suo Shi, produce the conductive sheet of 100 μm of thickness in addition with the condition identical with embodiment 1, measure resistance value.Show the result in table 1.
[table 1]
Claims (10)
1. a sheet material, it is the sheet material containing polytetrafluoroethylene, carbon black and graphite, it is characterized in that,
The standard specific gravity of described polytetrafluoroethylene is 2.14 ~ 2.28,
The total amount of carbon black and graphite exceedes 35 quality % of the total amount of polytetrafluoroethylene, carbon black and graphite.
2. sheet material as claimed in claim 1, wherein, the mass ratio of described carbon black and described graphite is 99/1 ~ 30/70.
3. sheet material as claimed in claim 1 or 2, wherein, described polytetrafluoroethylene is proplast or modified Teflon, is below the 0.02 quality % of whole polymerized unit in described modified Teflon based on the polymerized unit of modified monomer.
4. the sheet material as described in claim 1,2 or 3, wherein, the standard specific gravity of described polytetrafluoroethylene is 2.14 ~ 2.22.
5. the sheet material as described in claim 1,2,3 or 4, wherein, this sheet material is that described polytetrafluoroethylene, carbon black and graphite are by being total to condensation thus mixing.
6. the sheet material as described in claim 1,2,3,4 or 5, wherein, the average grain diameter of described carbon black is below 70nm.
7. the sheet material as described in claim 1,2,3,4,5 or 6, wherein, the average grain diameter of described graphite is less than 50 μm.
8. the sheet material as described in claim 1,2,3,4,5,6 or 7, wherein, described graphite is flakey or tabular.
9. an electrode, is characterized in that, it comprises the sheet material described in claim 1,2,3,4,5,6,7 or 8.
10. a fuel cell, is characterized in that, it has electrode according to claim 9.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012152336 | 2012-07-06 | ||
| JP2012-152336 | 2012-07-06 | ||
| JP2012-242022 | 2012-11-01 | ||
| JP2012242022 | 2012-11-01 | ||
| PCT/JP2013/068681 WO2014007397A1 (en) | 2012-07-06 | 2013-07-08 | Sheet, electrode and fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104412433A true CN104412433A (en) | 2015-03-11 |
Family
ID=49882147
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380035373.6A Pending CN104412433A (en) | 2012-07-06 | 2013-07-08 | Sheet, electrode and fuel cell |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20150200402A1 (en) |
| EP (1) | EP2871697A4 (en) |
| JP (1) | JP5500300B1 (en) |
| CN (1) | CN104412433A (en) |
| WO (1) | WO2014007397A1 (en) |
Cited By (2)
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| CN109690845A (en) * | 2016-09-07 | 2019-04-26 | 电化株式会社 | Electrode conductive composition and its electrode, battery are used |
| CN110306205A (en) * | 2019-07-09 | 2019-10-08 | 郑州大学 | A kind of gas-diffusion electrode and preparation method thereof |
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| JP2016012557A (en) * | 2014-06-02 | 2016-01-21 | 三菱レイヨン株式会社 | Gas diffusion layer and method for manufacturing the same |
| KR102356994B1 (en) * | 2015-06-19 | 2022-02-03 | 에스케이온 주식회사 | Anode material for secondary battery, and lithium secondary battery manufactured therefrom |
| CN110998750B (en) * | 2017-08-07 | 2021-08-20 | 电化株式会社 | Paste for flexible electrode and flexible electrode using same |
| JP7293901B2 (en) | 2019-06-20 | 2023-06-20 | 株式会社豊田中央研究所 | Granule, water-repellent layer and method for producing the same |
| CN114982023A (en) * | 2020-06-04 | 2022-08-30 | 蓝界科技控股公司 | Separator for fuel cell, precursor thereof and method for producing the same |
| DK180885B1 (en) | 2020-11-18 | 2022-06-14 | Blue World Technologies Holding ApS | Method of producing a self-supported electrode film in a wet process without organic solvent |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2871697A1 (en) | 2015-05-13 |
| JP2014112514A (en) | 2014-06-19 |
| JP5500300B1 (en) | 2014-05-21 |
| WO2014007397A1 (en) | 2014-01-09 |
| EP2871697A4 (en) | 2016-05-11 |
| US20150200402A1 (en) | 2015-07-16 |
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